Determination of the critical micelle concentration in simulations of surfactant systems

Santos, Andrew P.; Panagiotopoulos, Athanassios Z.

doi:10.1063/1.4940687

Title: Determination of the critical micelle concentration in simulations of surfactant systems

Journal Article · Thu Jan 28 00:00:00 EST 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4940687· OSTI ID:1469187

Santos, Andrew P. ^[1];

^[1]

Princeton Univ., Princeton, NJ (United States)

Alternative methods for determining the critical micelle concentration (cmc) are investigated using canonical and grand canonical Monte Carlo simulations of a lattice surfactant model. A common measure of the cmc is the “free” (unassociated) surfactant concentration in the presence of micellar aggregates. Many prior simulations of micellizing systems have observed a decrease in the free surfactant concentration with overall surfactant loading for both ionic and nonionic surfactants, contrary to theoretical expectations from mass-action models of aggregation. In the present study, we investigate a simple lattice nonionic surfactant model in implicit solvent, for which highly reproducible simulations are possible in both the canonical (NVT) and grand canonical (μVT) ensembles. We confirm the previously observed decrease of free surfactant concentration at higher overall loadings and propose an algorithm for the precise calculation of the excluded volume and effective concentration of unassociated surfactant molecules in the accessible volume of the solution. We find that the cmc can be obtained by correcting the free surfactant concentration for volume exclusion effects resulting from the presence of micellar aggregates. We also develop an improved method for determination of the cmc based on the maximum in curvature for the osmotic pressure curve determined from NVT simulations. Excellent agreement in cmc and other micellar properties between NVT and NVT simulations of different system sizes is observed. In conclusion, the methodological developments in this work are broadly applicable to simulations of aggregating systems using any type of surfactant model (atomistic/coarse grained) or solvent description (explicit/implicit).

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0002128

OSTI ID:: 1469187

Alternate ID(s):: OSTI ID: 1236409

Journal Information:: Journal of Chemical Physics, Vol. 144, Issue 4; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 42 works

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